Nu-sulfatoalkylsulfonamido substituted sigma-triazinyl amino anthraquinone dyestuffs



United States Patent ice jfiiiiii 3 157,652 N-SULFATGALKYLSUiJFGNAMED0 SUBEiTiTUTED s-TZWYL AMEND ANTHRAQUINUNE DYE- SO2 NH CH2)3N CHFCH1O S91H u i i ii a 1 st bl a l s t l a 5 HFCHFWSOSH ur 'eeran Jrazr iaeu e ase wizeran,as- T A signers to Ciba Limited, Basei: Switze i'iand, a company in the dyestufis of mvmfion the mazme budge 0f Switzerland represents a 2-chloro-tr1az1ne or a 2-phenyl-, phenoxyor No Drawing. Filed Feb. 14, W61, Ser. No. 89,127 phenylammo-l23:5-triazine bridge which is bound to an Claims priority, appiication Switzerland Mar. 1, 1951 anthraquinone radical through an amino group in each of 9 tliaims. (Ci. 260-449) 10 the positions 4 and 6. Of particular interest are dyestuffs of the formulae l I A -NHG o- NH (I)/ \EIJNHZ [H K 00NH7A1 l m-l and N A NHC o- NH- ('3/ \(|%NIEIZ jrl N\ /N k OONH-Ag \C jm-i I ia R The present invention relates to new anthraquinone vat in which n and m each represents a Whole number of at dyestuffs which contain two identical or different anthramost 2, A and A each stands for an anthraquinone radiquinone radicals linked together through a 1:3:5-triazine cal which may contain an acyl-amino or especially an bridge, and at least one sulfonic acid sulfato alkylarnide aroylamino group, and R for a phenyl radical, and at least group having at least 3 carbon atoms between the sulfate one or" the radicals A A or R contains a sulfamide group and the amide nitrogen atom. group of the type indicated.

The sulfonamide radical is advantageously attached di- The new dyestuffs are obtained by rectly to one of the two anthraquinone nuclei or to an 40 (a) Linking together two aminoanthraquinone dyearomatic nucleus which is bound to the triazine bridge. stuffs by reaction with an at least dihalogenated triazine Of particular interest are the vat dyestuffs containing compound and choosing the starting materials in such a the radical of the formula manner that at least one of the two anthraquinone nuclei and/ or one of the aromatic nuclei which may be present oml o g in the triazine compound contains a sulfonic acid sulfato- /m 11-2 /'q allcylamide group having at least 3 carbon atoms between q the suliato group and the amide nitrogen atom, or i I m gi 255 2 fi i g 5 (b) Esterifying corresponding deystutfs which contain 0 6 gm PS p a hydroxyl group instead of the sulfato group with a sulcm y fating agent, or

(c) Amidating anthraquinone vat dyestuffs, which cono, H onp oso rr tain two identical or different anthraquinone radicals linked together through a123z5-triazine bridge, and at least one sulfonic acid halide group, with a sulfatoalkylamine which contains at least 3 carbon atoms between the sulfato group and the amino group reacting with the sulfo halide group. SO NHCH CH OH2CH OSO H The anthraquinone compounds serving as starting ma- S0 .N .OH OH OH CH OSO H terials in modification (b) of the process and which con- Ha taidn a sglfonic acid-lilydroxyalkylaigge g??? thgltlype in icate LOI' examp e a group in TSOPNHOHQCHZCHNHCHZOSOsH which R represents an alkylene chain which may be inter- SO2 NHCH2CH2 O GHtCHtOSOaH rupted by hetero atoms and which has at least 3 carbon in which p is a whole number of at most 6.

The dyestuffs to be used according to the invention con- 55 tain advantageously at most 3 sulfonamide radicals, for example radicals of the formulae SOZ NH*OHQCHR N*CHECH2OS033 atoms, are advantageously obtained by reacting one of n ojmoso rr the sulfohalides used as starting material in modification -so,-NHoH,on -s ornornoso n (c) of the process with a hydroxyalkylamine, especially SOPNHCH,CH2 NH CH,CH20SO3H one of the formula SO NOH CH -NOH2CH1CH OS03H H 3E5 CHgCHzOSOaH 7 -SO NHOH CH NC H OH OS03H in which R has the meaning given above.

H3 The starting dyestuffs may contain the sulfonic acid halide group either in one or both of the anthraquinone radicals or in the phenyl radical which may be bound to the triazine nucleus. In the latter case the phenyl radical may be further substituted, for example by a hydroxyl or alkoxy group in ortho-position.

The preparation of the dyestuffs according to modification (a) of the process is advantageously carried out by condensing 2 identical or different anthraquinones which contain acylatable amino groups, with a dihalogen-triazine, more especially a 2:4-dichlorotriazine, which contains in 6-position a hydrogen atom, a halogen atom or an aryl radical; and in the aryl radical a sulfonic acid sulfatoalkylamide group of the type indicated must be present if no such sulfamide group is present in the aminoanthraquinones used.

When cyanuric chloride is used, a dianthraquinonylamino-chlorotriazine is obtained in which the chlorine at the triazine radical may be replaced by reaction with ammonia, or particularly an amine of the formulae NH; NH;

SO -NH-IP-OH or As examples of aminoanthraquinones there may be mentioned: l-aminoanthraquinone, l-amino-4-methoxyanthraquinone, laminoanthraquinone-6-sulfonic acid-N- (5 hydroxybutyl) amide, l aminoanthraquinone 7- sulfonic acid-N-(fi-hydroxybutyl)amide, 1-amino-4-benzoylaminoanthraquinone, l amino 5 benzoylaminoanthraquinone or 1amino-S-benzoylaminoanthraquinone. The latter may be substituted in the benzene radicals, for example by halogen atoms, alkoxy, alkyl, trifluoromethyl, sulfonamide or alkylsulfonyl groups. Such aminoanthraquinones also come into consideration which contain fused-on carbocyclic or heterocyclic rings, for example 4 amino anthraquinone 2:1(N) acridone, S-amino-l:9-is0thiazoleanthrone, 4- or S-amino-anthrapyridimine, also amino-dianthrimidecarbazoles, aminopyranthrones or aminodibenzanthrones. There may also be mentioned l:4-diamino-Z-acylanthraquinones, for example l:4diamino-2-benzoylanthraquinone, and particularly l:4-diamino-Zacetyl-anthraquinone of which it is known that under normal conditions the amino group only is acylatable in the 4-position.

The compounds containing the radical of the formula are advantageously treated with an agent yielding the sulfuric acid radical. This is advantageously carried out with concentrated sulfuric acid in the cold, for example between and 30 C., preferably with at least parts of sulfuric acid to 1 part of dyestuff. Sulfating may also be performed with oleum or chlorosulfonic acid or their addition compounds with tertiary bases or amides, for example pyridine, triethylamine or dimethylformamide.

The condensations according to the invention which are necessary in modifications (a) and (c) are preferably carried out in the presence of an acid-binding agent, such as an alkali metal hydroxide or alkali metal carbonate in an organic or aqueous medium.

The resulting dyestuffs may be isolated from the reaction mixture and processed to useful dry dyestuff preparations. Isolation is performed advantageously by filtration. The isolated dyestuffs may be dried by the addition of extenders having a neutral or weakly alkaline reaction; drying is preferably performed at not too high a temperature, if necessary under reduced pressure.

The new dyestuffs are suitable for dyeing many different materials, particularly for dyeing or printing textile materials of natural or regenerated cellulose, by the customary vatdyeing or printing processes. There are obtained level, strong dyeings and prints which are distinguished by excellent fastness to light and wetting.

It is assumed that in the dyebath or on the fiber under the influence of the alkali the radical OX is split off possibly with the formation of a heterocyclic 5- or 6-ring with the nitrogen atom of the sulfonamide group as hetero atom, that is to say the dyestuff is converted into an insoluble form.

As compared with conventional vat dyestuffs, the vat dyestuffs of the present invention have the great advan tage of being much more rapidly vattable. In addition, considerably fewer reducing agents are required for vatting. Their easy vattability makes the dyestuffs of the invention especially suitable for continuous dyeing.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated.

Example 1 4.1 parts of 4-aminobutanol-(l) in 20 parts of nitrobenzene are slowly added dropwise at -125 C. to 13 parts of the dyestulf sulfochloride of the formula SOsCl obtained by condensing the sulfochloride of 2-phenyl-4z6- dichlorotriazine-( 123:5) with 2 mols of l-amino-anthraquinone in nitrobenzene, in 140 parts of nitrobenzene and the mixture is stirred for 2 hours at 125 C. and 1 hour at C. After cooling, the dyestuff which has crystallized out in the form of small fine needles is filtered off, washed with benzene, alcohol and water, and dried.

10 parts of the resulting condensation product are introduced into parts of sulfuric acid of 96% strength at 0 to 5 C., and dissolved. The solution is then poured into approximately 800 parts of ice-water and filtered off. The moist filter cake is suspended in about 500 parts of water and neutralized with sodium hydroxide solution. The reaction product is then filtered off and dried in vacuo at 60 to 70 C.

The new dyestutf in its free acid state corresponds to N LEN IIIH- O It may be used as follows:

0.75 part of the dyestufl? is pasted with 250 parts of warm water. The resulting dyestuif suspension is added to a solution, heated to 50 C., of parts by volume of sodium hydroxide solution of strength and 6 parts of sodium hydrosulfite in 1750 parts of Water, vatting occurring immediately. In the resulting dyebath 50 parts of cotton are dyed for minutes at to C. with the addition of 40 parts of sodium chloride. After dyeing, the dyed goods are oxidized, rinsed, acidified, rinsed thoroughly again and soaped at the boil. A clear greenish yellow dyeing with excellent fastness properties is obtained.

The sulfochloride of 2-phenyl-4:6-dichlorotriazine- (1:3:5) may be obtained by sulfochlorinating Z-phenyl- 4:6-dihydroxy-triazine-(123:5) with chlorosulfonic acid and treating the sulfochloride of 2-phenyl-4z6-dihydroxytriazine with phosphorus pentachloride in phosphorous oxychloride.

Example 2 1.8 parts of 4-aminobutanol-(1) in 20 parts of nitrobenzene are slowly added dropwise at -125 C. to 7 parts of the dyestuff sulfochloride of the formula ll l 0 obtained by condensing the sulfochloride of 2-phenyl-4:6- dichlorotriazine-(1z325) with 2 mols of l-amino-S-benzoylaminoanthraquinone in nitrobenzene, in 100 parts of nitrobenzene, and the mixture is stirred for 4 hours at C. and for 1 hour at C. After cooling, the dyestufif which crystallizes out is filtered off, washed with benzene, alcohol and water and dried.

Conversion into the dyestuff of the formula is performed as described in Example 1. When applied,

to cotton and regenerated cellulose as described in Example 1, clear golden orange dyeings of excellent fastness properties are obtained.

Example 3 7 parts of the dyestulf sulfochloride of the formula obtained by condensing the sulfochloride of Z-phenyl- 50 4:6-dichlorotriazine-( 1:3:5) with 2 mols of 1:4-di-amino- Z-acetyl-anthraquinone in nitrobenzene, are condensed with 4-arnino-butanol as described in Example 2 and esterified with sulfuric acid as described in Example 1.

7 The new dyestuff of the formula dyes cotton and regenerated cellulose blue tints having excellent fastness properties.

Example 4 11.2 parts of the condensation product of 2 mols of 1- aminoanthraquinone with 1 mol of cyanuric chloride are heated at 180 to 185 C. in 120 parts of nitrobenzene with 14.6 parts of S-arninobenzene-(rt-hydroxybutyl)-sulfonamide for 6 hours with stirring. After cooling, the reaction mixture is filtered, washed with benzene, alcohol and water, and dried.

55 10 parts of the resulting condensation product are slowly introduced into 180 parts of sulfuric acid of 96% strength at O to 5 C. with stirring, and dissolved. The product is worked up as described in Example 1. The new dyestuff in its free acid state corresponds to the formula SO1-NH CHTCHTCHTCH1OSOJH IIIH 0 N I o NH-( JHN 0 II I II N 3,157,652 9 Example 5 which may be obtained by condensing m-nitro-benzene- 75 parts of 2: 4 bis (4, carboxy phenylamino) 6 ch10ro sulfochloride with N:N-dihydroxyethyl-propylenediamine- 1:3:54riazine are heated at in 200 parts of dry (1:3) and subsequent reduction, there is obtained after nitmbenzene i 8 parts f thionyl chloride and 5 esterification with sulfuric acid the dyestuif of the forpart of anhydrous pyridine for 3 hours with stirring. Af- 5 mula it t CHgCHg-OS O NEI ter ditsilling ofi the excess thionyl chloride in vacuo, 9.0 This dyestuif is vattable in the cold and dyes cotton parts of l-aminoanthraquinone are added at 100 C. and and regenerated cellulose yellow tints having very good the reaction mixture heated for 3 hours at 130 to 140 C. fastness properties.

After cooling to room temperature, the yellow condensa- Example 6 tion product is isolated by filtration, washed with nitro- 7.8 parts of 2:4 carboxy phenylamino) benzene and methanol and i chloro-l:3:5-triazine are dissolved in 200 parts of nitroparts of condensatlon Produat are suspenfied benzene with 8.0 parts of thionyl chloride by heating to m 100 parts of mtwbenzene and 6' of 110 C. in the course of 3 hours to form the correspond benzene'(a'hydroxybutyl)'sulfonamlde dlssolveq m 10 ing dicarboxylic acid chloride. After distilling ofi the parts of acetone are added. The reaction mixture is excess thionyl chloride in vacuo, 1071mm heated to 180 to 185 and Stirred for 6 hours at that nitro-anthraquinone are added at 100 C. and the mixture temperature. After cooling to room temperature, the reis heated for 6 hours at 130 to 10 parts of action product is isolated by filtration, washed with aceline are than added and the mixture stirred for 1 houn Ione and then Wlth Water fi dned- After cooling, the yellow condensation product is isolated 10 parts of the so'obtamed product are Slowly added by filtration and then reduced to the diarnine with excess to 9 of Sulfuric i mfmohydrate at 100 phenylhydrazine in ortho-dichlorobenzene 3.3 parts of and dissolved. The solution is then poured into about 40 the amine are then dissolvgd in 190 parts f boiling nitro 800 parts of ice-water and filtered off. The moist filter bfinzene and, ft coding to 130 c treated with a Cake is Suspended in 500 P of Water and f fi Warm solution of 2.8 parts of para-benzoic acid sulfodiwith sodium hydroxide solution, filtered and dried in chlo id in parts of nitrohenzene. 0.3 part of a hyvacuo at to C. drous pyridine is then added and the mixture heated for The dyestufi of the formula 4 hours at 130 C. while stirring thoroughly. After cool- N 3 0 NH-OC NHO G-NH- o O-HN 0 ll Q 1 ll 1 NH is vattable in the cold and dyes cotton and regenerated ing, the yellow dyestui'f is filtered oif and the filtrate stirred cellulose from an alkaline hydrosulfite vat fast yellow into parts of nitrobenzene at to C. 2.7 tints, parts of 4-arninobutanol in 30 parts of nitrobenzene If instead of using 6.0 parts of 3-aminobenzene-sulfonic are a ded drOpWise in the course of one hour, and heating acid-N-(a-hydroxybutyn-amide there is usgd an equi. 65 is continued stirring for 6 hOUIS at to 125 C. molecular proportion of 3-arninobenzene-sulfonic acidand for a further 2 hours at After Cooling, the

z r 1 yellowish brown dyestuif suspension is isolated by filtra- N 7 (N N bls hydroxyethyl) ammopropy amlde of the tion, washed with alcohol and water, and dried at 70 C.

formula in vacuo. 70 10 parts of the above product are dissolved slowly in C 200 parts of sulfuric acid monhydrate at 8 to 10 C. with 011 03 011 stlrring. The solution is then poured on to icewater and filtered off. The moist filter cake is suspended in 500 parts of water and neutralized with sodium hydroxide QHzCHzOH 75 solution, filtered and dried at 60 to 70 C. in vacuo.

The dyestuff of the probable formula dyes cotton and regenerated cellulose fast yellow tints.

If instead of using 2:4-bis-(4'-carboxyphenylamino)-6- chloro-1:3:5-triazine in this example there is used the same quantity of 2z4-bis (3-carboXyphenylamino)-6- chloro-1:3:5-triazine, a dyestuff is obtained having similarly good properties.

Example 7 8.4 parts of aminoacedianthrone are heated with 1.8 parts of cyanuric chloride in 150 parts of dry nitrobenzene for 9 hours at 170 to 180 C. with stirring until condensation is complete. 6.0 parts of 3-amino-oenzenesulfonic acid-N-(a-hydroxybutyD- amide diluted with 10 parts of dioxane are then added dropwise in the course of one hour. The reaction mixture is stirred for 6 hours at 180 C. and then cooled to room temperature. The dyestulf is isolated by filtration, Washed with alcohol and dried at 70 C. in vacuo.

10 parts of the so-obtained product are added slowly with stirring to 200 parts of sulfuric acid monohydrate at 8 to 10 C., and dissolved. The solution is then poured on to 1000 parts of ice-water and filtered off. The moist filter cake is suspended in 4-00 parts of water and neutralized with sodium hydroxide solution, filtered off and dried at to C. in vacuo.

The dyestult of the formula O 0 II I II I 0 NH $0 N803S0-(CI{1) 411N510:

Example 8 13.6 parts of the condensation product from 1 mol of 4: 6-dichloro-2-[ (5' )-benzoylamino-anthraquinonyl (1)- amino]-1:3:5-triazine and 1 mol of l-aminoanthraquinone (obtained by condensation in nitrobenzene at C.) are heated with 14.6 parts of 3-aminobenzene-(fi-hydroxybutyl)-sulf0namide for 6 hours at ISO-185 C. with stirring. After cooling, the reaction product is filtered 0ft", washed with benzene, alcohol and water and dried.

10 parts of the so-obtained condensation product are added slowly to parts of sulfuric acid of 96% strength at 0 to 5 C. with stirring, and dissolved. The product is worked up as described in Example 1. The new dyestufi? in its free acid state corresponds to the formula Cotton and regenerated cellulose are dyed by the method described in Example 1 golden yellow tints of excellent fastness.

13 Example 9 are added at to C. to 100 parts of concentrated 18.3 parts of the dyestufi of the formula sulfuric acid, and dissolved. The reaction solution is 01 I N/ 1?? o NH-C OC NHC C-NH II II H II I CO-HN O O NH--C O are heated in 180 parts of nitrobenzene with 14.6 parts 15 poured on to ice-water and filtered oif. The moist filter of 3-aminobenzene-(E-hydroxybutyl)-sulfonamide for 6 cake is suspended in about 1000 parts of water and neuhours at 180-185 C. with stirring. After cooling, the retralized with sodium hydroxide solution. After adding action product is filtered off, washed with benzene, alcohol 20 parts of sodium chloride, the reaction product is filand water, and dried. Y tered with suction and dried at to C. in vacuo.

10 parts of the so-obtained condensation product are 20 The new dyestufi in its free acid state corresponds to slowly added to 180 parts of sulfuric acid of 96% strength the formula 0 N l o NH-JJ CL-HN 0 nosso (0H2) r-NH-SO SO NH-(CH2)4OSO E II I 0 0 at 0 to 5 C. with stirring, and dissolved. The-product is Cotton and regenerated celluloseare dyed by the methworked up as described in Example 1. The new dyestuif od described in Example 1 golden orange tints of excellent in its free acid form corresponds to the formula fastness.

Cotton and regenerated cellulose are dyed by the meth- The dyestulf of Formula 1 may be prepared as follows: 0d described in Example 1 golden orange tints of excellent 14 parts of l-aminoanthraquinone-6-(4'-hydroxybutyl)- f t sulfonamide (prepared by condensation of l-nitrov E l 10 anthraquinone-6-sulfochloride with 4-aminobutanol and xamp e 60 reduction with sodium sulfohydrate in aqueous solution) 10 parts of the compound of the formula are heated in parts of nitrobenzene with 4.5 parts of 2-phenyl-4:6-dichlorotriazine-(123:5) for 5 hours at 150-155 C. with stirring. After cooling the crystalline dyestutf is filtered off, Washed with alcohol and dried.

What is claimed is: 1. A vat dyestuff of the formula 5 in which A and A each is a-anthraquinolyl, m, n and p 4. The vat dyestulf of the formula each represents a whole positive number up to 2 and R represents an alkylene chain containing 4 to 5 carbon atoms and X is a sulfo group bound to the -O- atom through its sulfur atom. 25

2. A dyestuff as claimed in claim 1 which contains a benzoylamino group in at least one of the a-positions of the anthraquinone radicals A and A 3. The vat dyestutf of the formula i 5. The vat dyestuff of the formula 6. The vat dyestuff of the formula References Cited in the file of this patent UNITED STATES PATENTS Wieners Mar. 19, 1935 Barker et a1. Apr. 4, 1961 Putter et a1. Apr. 10, 1962 Wegmann et al. July 10, 1962 Kantner et a1. July 24, 1962 Wedemeyer et a1. Nov. 2, 1962 FOREIGN PATENTS Belgium June 13, 1958 Great Britain Oct. 16, 1957 OTHER REFERENCES Wegmann: TeXtil-Praxis, October 1958, p. 1056.

1 7. The vat dyestuff of the formula SOgNH(CHz)4-OSO H 1 994 602 E q 5 2,978,289 3,029,123 I 3,043,650 3,046,075 G 3,066,005 ll 5 I 563,199 II Nat am ll 784,926

II II 0 0 Hess et al.: Nature, vol. 183, page 260, Jan. 24, 1959.

Lubs: Chemistry of Synthetic Dyes and Pigments,"

8. A vat dyqstuff of the formula 9. A vat dyestufi of the formula 20 1955, pages 522 and 612.

NilO SO-(OHz) 413N80 Pater 1t No 3,15%652 UNITED STE'IESI'EATEFIT OFFIQE 4 CERTIFICATE OF CORRECTION November 17, 1964 Kur gWeber et a1. I

It is hereby certified that error eppeers in the above numbereci patent requiring correctionand that ..the 'seiid Letters Patent should read as correeted below. v

I Column 15,. lines 6 to 2O the upper left-handportion' of the formula should appearas shown below instead of -as in the pate nt: I u I same column 15' line 21 for "q-anthra'quino1y1" reed q-anthraquinonyl Signed and sealed this 4th day of May 19.65.,

(SEAL) Attest:

ERNEST w. SWIDER EDWARD'J. BRENNER Attesting Officer v Commissioner of Patents 

1. A VAT DYESTUFF OF THE FORMULA 